Production of disinfectants and pest exterminating agents



Patented Feb. 15, 1944 PRODUCTION OF DISINFECTANTS AND PEST EXTERMINATIN G AGENTS Karl Wilhelm lbosen mund, Kiel, Germanyi vested in the Alien Property Custodian No Drawlng.' Application June 28, 1939, Serial No. 281,683. In Germany June 28, 1938 5 Claims. (o 167- 431) This invention relates to the production of dis?- infectants and pest exterminating agents on the basis of aromatic hydroxyl compounds.

It is known that'com-positions of phenolic character, such as substituted phenols, naphthols, oxydiphenlymethanes and the substitution prodnets of such compounds, possess excellent disinfecting power which, however, cannot be fully utilized for the reason that they are insoluble or very slightly soluble in water. It has been proposed to eflect a solution of such compounds with the aid of dissolving partners like salts or the salicylic and cresotic acid and others, and- These particularly fattyaoid and resin soaps.

soaps possess not only a great carrying capacity for. many phenols but also great capillary activ ity .and good. wetting-out power and therefore also penetrativity. Unfortunately, it was found out, however, that all such systems; especiallyif they show an alkaline reaction, tend to-reduce the efficacy of the phenols, in consequence whereof the action of the agents on parasites is considerably weakened.

The in'vention proposes to use as dissolving aids or dispersion agents the salts of secondary phosphoric acid esters of the general formula in which Ph and Ph' indicate a phenol, naphthol, I

oxydlphenylmethane of their substituted derivatives, above all their halogen-substituted derivatives, and Me stands for an alkaline metal or a nitrogenous base like ammonium, triethano1a-; mine-etc, Aromatic hydroxyl compounds of this kind, are briefly referred to below as phen ols.

Such bisphenolphosphates are capable not only of dispersing phenols \or even of acting as dissolving partnersto keep them in solution but are also active in lowering surface tension and in aqueous solution possess considerable wettingout power. Above all, however, they have per .se a remarkable bactericidal and fungicidal as well as a high disinfecting and pest destroying eil'e'ct. Combined with phenols, they act asdissolving aids and dispersion agents and not only do not reduce the effectiveness 01' the phenols but positively increase it, frequently to such a point that the effects are potentiated and are over- 5 additive.

A number of useful components are mentioned below without intending to restrict the invention to them. I

Phenols within the meaning of the invention which are dispersed or colloidallyzdissolved but 5 which may serve also for building up bisphenolphosphates are for instance phenol, naphthol, oxydiphenylmethane and oxyquinoline and particularly the substitution products of these phenols, as cresols, xylenes,-'thymol, carvacrol,

substituted phthols and oxydiphenylmethane like benzylc esoland others. Particularlysuitable appear to be combinations in which at least one constituent (dispersing medium or dispersed phenol) contains as a minimuma ha'lophenol like chlorophenols, bromophenols, diand trichlorophenols, chloronaphthols, chlorooxydiphenylmethanes like benzychlorophenols and dichlorophenolmethanes and, above all, the extraordinarily effective substituted, i. e., alkylated, halophenols, such as chlorocresols, chlorothymol, chloroisothymol, benzylchloroeresol, etc.

When these phenols are to be used as dispersing media or dissolving aids in the form of bisphenolphosphates, they are converted by means of phosphoric acid or its derivatives, the chlor- 3 ides or esters. Conversion can be effected in known manner, and the surprising fact discovered is that even themor complex alkyl halide phenols can be smoothly converted into the corresponding bisphenolphosphates. It is further possibleto produce first monophenolphosphates in known manner and subsequently convert them into bisphenolphosphates so as to have an opportunity of incorporating therein difierent phenols, or to build up first the triphenolphos phates and to saponify them later on in suitable manner to form bisphenolphosphates, which may be eilected by the'action oi saponifying acid and, above all, through saponifyingbases. The following examples recite by way of explanation some of the. methods of production without, however, restricting the invention to the disclosures made.

Example 1 From chlorothymol (excessl and phosphorous oxychloride, possibly with the addition of a diluent like nitrobenzene, xylene, etc., trichlorothymolphosphate is produced in known manner,

possibly while adding a catalystlike aluminium chloride, iron chloride, zinc chloride, or the like. This compound may 'be produced also with the aid of sodium chlorothymol or by converting chlorothymol in alkaline aqueous or aqueous acetonic solution with phosphorous oxychloride or even from phosphoric acid by conversion with chlorothymol or from an ester oi phosphoric acid, possibly the triethylester, by conversion with chlorothymol. f a

/aoth mol trichlorothymolphosphate, melting point 84f, is dissolved in alcohol and after addition of lroth mol potassium hydroxide heated at boiling point for 10 hours. The alcohol 'is y then evaporated, the residue taken up'in water a and the solution freed from split oil chlorothymol. The bischlorothymolphosphate of potassium can b obtained from the solution by salting out with potassium carbonate. The free acid'can' be obtained by acidulatins the salt 80- -an excellent disinfectant.

' phenol.

lution by means of hydrochloric acid, extracting the bischlorothymolphosphoric acid with ether and recrystallizing the isolated acid from petroleum ether mixtures; it has a melting point of 134;

To the sodium or potassium salt of this acid a phenol can be added to the easily ascertainable extent of the carrying capacity of a solution of these salts in water. Preferably, chlorothymol is used whil equimolecular quantities are brought into solution and filtered off from smaller quantities of'undissolved matter. The solution or dispersion may be produced also .by retaining the amount of chlorothymol obtained during the preparation of the compound instead of separating it, this being probably the simplest manner of producing mixtures according to the invention.

Example 2 0.6 mm. at 123 to 125 C. and the bischlorocarvacrolphosphoric-monochloride at 190 to 192 C. The yield of dichloride amounts to approximately g. and that of monochloride to about 24 g. The dichloride can be converted again into a bisphenol compound with the aid of chlorocarvacrol or another phenol, and the monochloride is decomposed with water to form afree acid. The sodium salt is soluble in ether.

To a solution of sodium or ammonium salt in .ether is added approximately the semimolar amount of 4-chlorophenol or chlorothymol,

whereupon the mixture is heated for some time and then evaporated to dryness. The residue is Example 3 100 parts by weight bischlorothymolphosphate of potassium, 50- parts by weight commercial p-chloro-m-cresol and 100 parts by weight ethanol are dissolved in one another while being slightly heated. A 1:200 dilution in water kills suspensions of bact. coli. com. in about minutes, a 1:1000 dilution kills instantly Staphyloc. aureus and a 1:4000 dilution immediately destroys suspensions of streptococci. Even ground spores are instantly killed by a'1;400 dilution and after 5 to 10 minutes by a 1:1000 solution. The solutions of the disinfectants in water prove to be typical colloidal solutions of excellent stability. Separation might happen with salts causing hardness of water, which may be prevented, however, by the addition of known substances like sodium tetrametaphosphate and similar isopolyphosphates, Turkey-red oil, sodium octadecenoylmethylaminoethanesulfonate, sodium dodecanole sulfate, etc.

xa ple 4 thymolphosphate and 20 parts by weight commercial chlorothymol are together dissolved in ether and separated again as mixture by rapid evaporation of the ether. This mixture is dried in the vacuum. An aqueous solution of the mixture applied to vegetable germs show about the same efl'ect as the preparation of Example 3. The efl'ect upon spores was even considerably greaterin spite of a smaller content of free Example 5 give a clear solution. The action of an aqueous solution obtained by dilution is only slightly less than that of Example 3.

If technical cresol mixtures serve for conversion into bisphenolphosphates which are used as carriers for such cresol mixtures or other phenol, the mixtures obtained will not be fully equal in effectiveness to those mentioned above but will be very cheap. Monophenolphosphates appearing during production need not be separated, as they do not cause any trouble but on the con-' trary add to the general effect; As stated before, the simplest procedure is to convert the phenols only partly into bisphenolphosphate, and to use this, possibly together with monophenolphosphates that have appeared, as dispersion agent or dissolving aid for the non-phosphorylated portion of the phenols. The possibility of producing mixed bisphenolphosphates from difierent phenol components and using them has been mentioned already. For example, from 'oxydiphenyletherphosphatedichloride and chlorothymol in presence of pyridine a mixed bisphenolphosphatemonochloride was obtained from which the highly active salt can be produced.

Example 6 10 parts by weight potassium bischloroisothymolphosphate and 2 g. (1) chlorine (2) naphthol or 2 g. oxydiphenylmethane are dissolved in 12 parts by weight alcohol. The resulting solution has a strong bactericidal elfect.

I claim: K

1. Process of producing disinfectants and pest exterminating agents, comprising saponifying triphosphates of phenolic compounds selected from the group consisting of phenols, alkylated phenols, halogen-substituted phenols and halogenand alkyl-substituted phenols by adding a saponifying agent thereto in order to form bisphenolphosphates and free phenols, the latter.

being held in solution or dispersion by the bisphenolphosphates.

2. Process of producing disinfectants and pest exterminating agents, consisting in producingone of the phenols being a halogen-substituted aromatic hydroxyl compound.

, 5. Disinfectants and pest exterminating agents, consisting of a watery solution of phenols, some of said phenols being bisphenol phosphates serving as solubilizing agent for the others, at least one of the phenols being a halogen-substituted and alkyl-substituted aromatic hydroxyl compo n 1 KARLIWILHEIM ROSENMUND. 

